Preparation and characterization of UV-cured acrylic nanocomposites based on modified organophilic montmorillonites

UV-cured nanocomposites have been prepared through the photopolymerization of the acrylic resin BEMA (Bisphenol A ethoxylate dimethacrylate) added with organophifilic montmorillonites. Two types of commercially available nanoclays namely Cloisite 30B and Cloisite Na⁺ were further modified with organic compatibilizers (dodecylsuccinic anhydride, octadecylamine, octadecanoic alcohol and octadecanoic acid) in order to increase their basal spacing and improve the dispersion in the acrylic matrix. The modification with the organic compatibilizers determined an increase of the interlayer distance, as revealed by XRD (X-Ray Diffraction) analysis. The different types of the modified nanoclays were then dispersed in BEMA monomer at 5% m/m concentration and UV-cured in order to prepare the nanocomposites. XRD measurements performed on the nanocomposites showed a slight increase of the interlayer distance indicating the formation of intercalated structures. The photopolymerization reaction was monitored through real-time FT-IR (Fourier Transform Infrared Spectroscopy) in order to check any influence of the nanofillers on the cure kinetics. The nanocomposites were investigated by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetric) analyses and compared to the neat UV-cured resin. The presence of the nanofillers did not influence the glass transition temperature (T_g) of the acrylic resin; in addition an increase of the thermal stability in air of the nanocomposites was evidenced through TG analysis.     

The swelling of organophilic montmorillonites in liquids

The crystalline swelling of amine montmorillonites is shown to take place in certain liquids. The relation between the steric requirements of the intercalated molecules is discussed.     

Intercalation effects in LDPE/o-montmorillonites nanocomposites

Typical montmorillonite clays (Cloisite^® Na⁺, Cloisite^® 30B) were modified by treatment with octadecyl ammonium chloride (ODC) and successive additions of octadecylamine (ODA). XRD analyses of the modified clays indicated an increase of the basal spacing of the (0 0 1) planes depending on the ODC or ODA additions.Nanocomposites were prepared by dispersing the modified clays (3% w/w concentration) in LDPE, using a Brabender mixer. XRD measurements of the obtained products indicated in some cases the achievement of intercalation effects, which were confirmed by TEM analysis.Some thermal, mechanical, dynamic-mechanical and rheological properties were evaluated and correlated to the degree of intercalation.     

Wetting and adsorption on organophilic illites and swelling montmorillonites in methanol-benzene mixtures

Adsorption and immersion were studied simultaneously in methanol-benzene mixtures on non-swelling organophilic illites and swelling organophilic montmorillonites. From the combination of adsroption and calorimetric data, equations were proposed for the determination of the adsorption capacity and the molar enthalpies of wetting differences, if the adsorption layer behaved ideally. From the experimental enthalpy isotherms of wetting and the enthalpy functions related to the ideal behaviour of the layer, qualitative conclusions were drawn on the excess enthalpy of the adsorpition layer. It was again established that the adsorption layer composed of alkyl chains, benzene and methanol has a regular cluster structure in certain concentration ranges, which breaks at higher methanol concentrations. This change is reflected by a significant endothermic peak of the differential molar enthalpy.For the organophilic montmorillonites, the enthalpy of swelling was determined separately as a function of the composition. The non-swelling organophilic illites were chosen as a reference system.Dedicated to Professor Dr. Armin Weiss on the occassion of his 60th birthday.     

Preparation and characterization of nylon 66/montmorillonite nanocomposites with co-treated montmorillonites

In this paper, a new type of organophilic montmorillonites, co-treated by octadecylammonium and aminoundecanoic acid, were synthesized and applied to prepare nylon 66/montmorillonite nanocomposites via melt compounding in a twin extruder. WAXD and TEM characterization indicate that a disordered structure was derived and the montmorillonite platelets dispersed in nanoscale in the nylon 66 matrix. The nanocomposites with co-treated montmorillonite display comparatively higher strength and modulus compared to nylon 66 matrix.     

Preparation and properties of compatibilized LDPE/organo-modified montmorillonite nanocomposites

Nanocomposites based on low density polyethylene, containing of 3 or 6 wt.% of organo-modified montmorillonite nanoclay (MMT-ODA) and maleic anhydride grafted low density polyethylene as a compatibilizer were prepared by melt mixing and characterized. Exfoliation of silicate layers was achieved, as confirmed by X-ray diffraction and transmission electron microscopy. The compatibilized nanocomposites exhibit improved thermal stability in air as compared to neat polyethylene and nonexfoliated MMT-ODA composite. The crystallinity and crystallization kinetics of polyethylene matrix is not affected significantly by the presence of MMT-ODA clay. Drawability of the compatibilized nanocomposite with 6 wt.% of MMT-ODA is similar to neat polyethylene, whereas the composition having the same amount of MMT-ODA, without compatibilizer, exhibits poorer drawability. Scanning electron microscopy and density measurements of drawn samples indicate the existence of pores in noncompatibilized composite while no pores and good adhesion to MMT-ODA are found in compatibilized nanocomposites.     

Catalyzing carbonization function of ferric chloride based on acrylonitrile-butadiene-styrene copolymer/organophilic montmorillonite nanocomposites

A study on the Lewis acids-type transition metal chloride (FeCl₃) catalyzing carbonization based on acrylonitrile-butadiene-styrene copolymer (ABS)/organophilic montmorillonite (OMT) nanocomposites has been achieved. The results of XRD, TEM and HREM experiments show the formation of intercalated structure. The thermal stability of the nanocomposites slightly decreases, but the char residue remarkably increases compared with pure ABS. Meanwhile, it is found that the loading of FeCl₃ leads to crosslinking of ABS, promotes the charred residue yield and catalytic graphitization effect. The structure and morphology (XRD, HREM, SAED and LSR) of the purified char residue approve further the presence of graphite sheets. The possible catalyzing carbonization mechanism is composed of three prominent aspects. The first is the catalyzing effect of FeCl₃ promoting the crosslinking of polymer. The second is the Hofmann degradation of OMT, whose degraded products have opposite role in promoting crosslinking reactions and the last is the nano-dispersed clay layers. The gas barrier properties of clay stop or reduce the release of the pyrolytic products, which have been dehydrogenated for more time and aromatized to form char.     

Homoionic inorganic montmorillonites as fillers for polyamide 6 nanocomposites

The homoionic montmorillonites Ca-MMT, Mg-MMT, Ba-MMT and Ca-MMT intercalated with ε-caprolactam - Ca-MMT·CL were prepared from commercial Na-MMT and characterized by WAXS and TGA. They were used as fillers for nanocomposites of polyamide 6 synthesized either by anionic polymerization of ε-caprolactam (monomer casting) or by melt blending. WAXS analysis showed that the intercalation of MMT by the polyamide was complete for all nanocomposites, with only a very small fraction of exfoliated platelets being detected by TEM. The decrease in the number of layers in the MMT tactoids suggests that tactoid splitting was lower for the blended nanocomposites than for the polymerized ones. Both the rate of polymerization and the polyamide yield in the nanocomposites were comparable to those of an unfilled system. The MMT fillers, the density of which was more than twice that of the ε-caprolactam in which they were suspended, sedimented during the first stage of polymerization. TGA was used to determine the degree of sedimentation at various levels of the resulting mold. In line with the coordination of polyamide chains to the surface cations of MMT particles, the sedimentation level increased in the following sequence: Mg-MMT < Ba-MMT < Ca-MMT·CL << Na-MMT. Ca-MMT was found to be the only non-sedimenting filler suitable for use in the synthesis of polyamide nanocomposites by either monomer casting or the use of reactive injection molding (RIM) technologies.     

Comparative analysis of nanocomposites based on polypropylene and different montmorillonites

Nanocomposites of polypropylene (PP) were prepared by melt mixing using maleic anhydride modified polypropylene (PPg) and different organophilic montmorillonites (OMMT). The selected organo-modified clays differ in their initial particle size, amount and type of surfactant and/or their cation-exchange capacity. All composites have 80, 15 and 5 wt% of PP, PPg and OMMT, respectively. The materials were characterized using TGA, XRD, SEM and rotational rheometry. Cloisite 15A, Cloisite 93A, Nanomer I44 and a bentonite modified with octadecylammonium (B18) display intercalation and exfoliation after mixing and annealing and produce nanocomposites with different degrees of ‘solid-like’ rheological behavior. The composites based in Cloisite 15A and Nanomer I44, which use the same intercalant, show very similar phase structure and rheological response, regardless of the origin and initial characteristics of the clays. These nanocomposites are the most affected by the thermal history during rheological characterization in the molten state. On the other hand, Cloisite 10A and Cloisite 30B display collapse of the silicate layers after compounding with no evidence of exfoliation.     

LDPE/EVA/graphene nanocomposites with enhanced mechanical and gas permeability properties

In the present work, graphene oxide (GO) and reduced graphene oxide (RGO) were incorporated at low‐density polyethylene (LDPE)/ethylene vinyl acetate (EVA) copolymer blend using solution casting method. Monolayer GO with 1‐nm thickness and good transparency was synthesized using the well‐known Hummers's method. Fourier transform infrared and X‐ray photoelectron spectroscopy data exhibited efficient reduction of GO with almost high C/O ratio of RGO. Scanning electron microscopy showed the well distribution of GO and RGO within LDPE/EVA polymer matrix. The integrating effects of GO and RGO on mechanical and gas permeability of prepared films were examined. Young's modulus of nanocomposites are improved 65% and 92% by adding 7 wt% of GO and RGO, respectively. The tensile measurements showed that maximum tensile strength emerged in 3 wt% of loading for RGO and 5 wt% for GO. The measured oxygen and carbon dioxide permeability represented noticeably the attenuation of gas permeability in composite films compared with pristine LDPE/EVA blend. Copyright © 2015 John Wiley & Sons, Ltd.     

Polymer-clay nanocomposites: Free-radical grafting of polyacrylamide onto organophilic montmorillonite

This paper is an account of the experiments on grafting polyacrylamide onto organophilic montmorillonite. Cloisite 20A was reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety. Since the reaction liberates HCl, it was performed in the presence of sodium hydrogencarbonate to prevent the exchange of quaternary alkyl ammonium cations with H⁺ ions. Only the silanol groups on the edge of the clay react with vinyltrichlorosilane. The product maintained the same basal spacing as the precursor. The radical polymerization of the product with acrylamide as a vinyl monomer leads to chemical grafting of polyacrylamide onto montmorillonite surface. The homopolymer formed during polymerization was Soxhelt extracted from the grafted organoclay. Chemical grafting of the polymer onto Cloisite 20A was confirmed by IR spectroscopy. The interlayer and surface changes of the clay in the prepared nanocomposite materials and the grafted nano-particles were studied by XRD and SEM. Intercalated nanocomposites were obtained for clay contents of 3-7% and agglomeration occurred at higher clay loadings. The nanocomposites were studied by thermogravimertic analysis (TGA) and dynamic mechanical analysis (DMTA).     

TGA/FTIR studies of segmented aliphatic polyurethanes and their nanocomposites prepared with commercial montmorillonites

Nanocomposites prepared with segmented polyurethane (SPU) and commercially available nanoclays (Cloisite™ Na⁺, Cloisite™ 15A, Cloisite™ 30B) were studied using thermogravimetric analysis coupled with Fourier Transform Infrared Spectroscopy (TGA/FTIR). The results showed that the thermal degradation of unfilled SPU and the 4, 6 and 10 wt% hand mixed nanocomposites occurred in two stages being the first due to degradation of hard segments and the second due to the degradation of soft segments. It was also found that the thermal stability of these nanocomposites was not improved by increasing nanoclay concentration except for SPU/Cloisite™ 15A nanocomposites were a 40 °C increase was observed. In a similar manner, FTIR spectra of the evolved gases obtained after the thermal degradation of these nanocomposites were qualitatively similar to the unfilled polymer except in those containing Cloisite™ 30B where isocyanate absorptions were detected. In contrast, SPU/Cloisite™ 30B nanocomposites prepared by in-situ polymerization, exhibited higher thermal stability than the corresponding hand mixed nanocomposites. In addition, these nanocomposites exhibited the presence of carbon dioxide in the evolved gases during its second degradation stage which was not observed in the hand mixed nanocomposites. In this case, it can be said that the presence of clays in the nanocomposites has a significant effect on the thermal degradation pathways.     

Influence of the intercalated cations on the surface energy of montmorillonites: consequences for the morphology and gas barrier properties of polyethylene/montmorillonites nanocomposites

Organically modified montmorillonites obtained by cation exchange from the same natural layered silicate were studied. The surface properties of the pristine and a series of organically modified clays were determined by inverse gas chromatography and the water adsorption mechanisms were studied by a gravimetric technique coupled with a microcalorimeter. A significant increase of the specific surface area, a decrease of the water adsorption, and a decrease of the dispersive component of the surface energy were observed when the sodium cations of the natural montmorillonite were exchanged for a quaternary ammonium. Slighter differences in surface properties were observed, on the other hand, between the different types of organically modified montmorillonites. Indeed, similar dispersive components of the surface energy were determined on the organoclays. Nevertheless, the specific surface area increased in the range 48-80 m(2)/g with increasing d-spacing values and the presence of specific groups attached to the quaternary ammonium, such as phenyl rings or hydroxyl groups, led to some specific behaviors, i.e., a more pronounced base character and a higher water adsorption at high activity, respectively. Differences in interlayer cation chain organization, denoted as crystallinity, were also observed as a function of the nature of the chains borne by the quaternary ammonium. In a later step, polyethylene-based nanocomposites were prepared with those organically modified montmorillonites. The clay dispersion and the barrier properties of the nanocomposites were discussed as a function of the montmorillonite characteristics and of the matrix/montmorillonite interactions expected from surface energy characterization.     

Evidences of macromolecular chains confinement of ethylene–propylene copolymer in organophilic montmorillonite nanocomposites

A random ethylene–propylene copolymer (EPM) functionalized with grafted diethylsuccinate groups was melt blended with increasing amount (to 20 wt%) of organophilic montmorillonite (OMMT) to prepare nanocomposites with different morphologies as evidenced by XRD and TEM analysis. All the nanocomposites were treated with boiling toluene that did not extract a significant amount of EPM. The increase of not-extracted EPM with the increasing quantity of OMMT suggested strong interactions of the polymer chains with the inorganic substrate. The DSC measurements of nanocomposites and the corresponding insoluble residues revealed a higher T_g values with larger amount of inorganic particles. The dielectric relaxation analysis confirmed the evidence of strong interactions among montmorillonite and the polar diethylsuccinate groups for the macromolecules trapped due to the presence of the inorganic layers. The results were discussed with reference to their relevance as an evidence of nanoconfinement at polymer clay interface and correlated with the clay basal distance variation due to the intercalation process.     

Modified montmorillonites as potential NO decomposition catalysts: Characterization by temperature-programmed reduction

Na-montmorillonite has been modified by ion exchange of simple Fe³⁺ or Keggintype cations obtainedvia the partial hydrolysis of AlCl₃ or the co-hydrolysis of AlCl₃+FeCl₂ mixture, in order to prepare catalysts for NO decomposition. Temperature-programmed reduction, the most important characterizing method in this work, revealed that isomorphous substitution of iron for aluminium was not feasible, instead, co-hydrolysis and co-pillaring occurred, resulting in Fe,Al mixed pillared clays.     

聚乙烯在天然橡胶／聚乙烯共混体系中的结晶行为

本工作主要利用DSC、x-射线衍射、小角激光光散射以及偏光显微镜等方法,对天然橡胶/低密度聚乙烯共混体系(NR/LDPE)中LDPE的晶体结构、结晶度、球晶尺寸和形态、微晶尺寸、成核过程以及结晶动力学等方面进行了研究,得到了一些有意义的结果。     

Equilibrium thermal behavior and morphology of organophilic montmorillonite/poly(ε‐caprolactone) nanocomposites

With differential scanning calorimetry, we have demonstrated a peculiar behavior under equilibrium conditions of neat poly(ε‐caprolactone) and its organophilic montmorillonite nanocomposites. In particular, in the determination of the equilibrium melting temperature by the extrapolation of the data of the melting temperature (T_m) versus the crystallization temperature (T_c), a bimodal trend has been observed. At the lower T_c's, the data of T_m follow a constant trend, whereas at the higher ones, the usual increasing trend has been obtained. Morphological observations by atomic force microscopy (AFM) have provided evidence of two different crystalline morphologies for the lower and higher T_c ranges. Moreover, AFM has shown that the thermal treatments strongly influence the clay dispersion in the polymer matrix. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 22–32, 2006     

Preparation, characterization and application of polymeric diols with comb-branched structure and their nanocomposites containing montmorillonites

The polymeric diols with comb-branched structure (CPD) and their nanocomposites containing montmorillonites (MMT) were prepared through three-step reaction on basis of molecular design. The effect of experimental parameters, such as molar mass of oligomer polyols, catalysts and MMT on conversion of -NCO group during polymerization was investigated by utilizing FTIR to measure content of -NCO group varied as reaction time. In addition, the structure of comb-branched polymeric diols was characterized by FTIR and ¹H NMR. The results show that the comb-branched chains contain reactive CC double bonds in CPD. The nature of dispersion of montmorillonites in CPD was characterized by X-ray diffraction. The results show that Na⁺-MMT is exfoliated and organo-MMT is intercalated in CPD via in-situ polymerization. Finally, the properties of water-borne polyurethane modified with CPD or CPD/2T-MMT nanocomposite were compared with those of common water-borne polyurethane, and the comb-branched chains and 2T-MMT improve the properties of water-borne polyurethane.     

Viscoelastic behavior of epoxy prepolymer/organophilic montmorillonite dispersions

Dispersions of a bisphenol A‐based epoxy resin with an organophilic montmorillonite (Nanofil 919) were studied by X‐ray diffraction and oscillatory shear rheometry. X‐ray studies reveal that the clay is intercalated by the epoxy and forms stable dispersions. The viscoelastic behavior of the nanodispersions was measured as a function of the Nanofil concentration and temperature. An increase in both G′ and G″ moduli was detected as the concentration increases. Furthermore, a transition from a liquid‐like behavior, at low temperatures, to a solid‐like behavior, at higher temperatures, was observed for all the samples. This transition is accounted for the formation of a percolated structure of interconnected tactoids through hydrophobic interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1837–1844, 2008     

Partially exchanged organophilic bentonites

Phenol is a pollutant that has caused many problems even when present in low concentrations and still represents an environmental problem with difficult solution. This paper presents a study of phenol adsorption by organophilic clays, obtained from aVerde Claro bentonitic clay, from Bravo, Paraíba State, Brazil, at different partial cation exchange degrees with hexadecyltrimethylammonium (HDTMA) chloride, at increasing reacting ratios, from 20 to 120 mmol/100 g of clay, which were characterized in a previous paper. By using Freundlich isotherms obtained for each case, which presented the best correlation coefficients with experimental data, it can be seen that for equilibrium concentrations up to 0.53 mmol L⁻¹ of phenol, the adsorptive capacity decreases for organophilic bentonites obtained at cation exchange degrees higher than 80 mmol/100 g of clay. This indicates that in these cases, the higher is the exchange by organic cation, the higher is the difficulty for the phenol diffusion and sorption in the interlayer space of the organophilic clays. For higher equilibrium concentrations, the maximum adsorption occurs for the organophilic bentonite obtained at 100 mmol/100 g of bentonite exchange.